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In 1210 a group of Cathars sought refuge in the village after the massacre at Béziers during the Albigensian Crusade. The village was besieged by Simon de Montfort, 5th Earl of Leicester. The attacking army besieged the village for six weeks before it capitulated. They set up four trebuchets around the fortification: three to attack the village, and the largest, Malevoisine, to attack the town's water supply. Eventually the commander of the 200-strong garrison, Viscount Guilhem of Minerve, gave in and negotiated a surrender which saved the villagers and himself after the destruction of the town's main well. However, 140 Cathars refused to give up their faith and were burned to death at the stake on 22 July.

Minerve has been selected as one of Les Plus Beaux Villages de France ("The Most Beautiful Villages Of France"). Historically, the village has been the capital of the Minervois wine region. The main bridge leading into the village is closed to all passenger vehicles not owned by residents of Minerve. Of all of the original fortifications, only a slender octagonal tower, known locally as the Candela, survives.